Plant hormone carboxylic acid salts of aliphatic polyamines

ABSTRACT

Plant hormone carboxylic acid salts of certain aliphatic diamines, triamines and tetraamines having at least 6 carbon atoms in an aliphatic radical thereof, useful as herbicidal agents.

1 States Patent [191 Retell et a1.

[11] assimo *Deofi, 1074 PLANT HORMONE CARBOXYLlC ACID SALTS 0F ALlPHATlC POLYAMINES Inventors: Richard A. Real, Hinsdale; Walter W. Abramitis, Downers Grove, both of ill.

Assignee: Ak'zona Incorporated, Ashville, N.C.

Notice: The portion of the term of this patent subsequent to Aug. 8, 1989, has been disclaimed.

Filed: Apr. 21, 1970 Appl. No.: 30,608

Related US. Application Data Continuation-impart of Ser. No. 581,725, Sept. 26, 1966, Pat. No. 3,683,010, which is a continuation-in-part of Ser. No. 300,108, Aug. 5, 1963, abandoned.

US. Cl 260501.16, 260/319.1, 260/442 R, 260/501.1l, 260/5012, 260/50l.17, 71/96, 71/97, 71/113, 71/115, 71/116, 71/117 Int. Cl. C07c 87/14 Field of Search 260/50l.l6, 501.17, 501.2, 260/319.1, 501.11; 71/114, 115, 116, 117

OTHER PUBLICATIONS Oe sterreichische Mineraloelverwaltung A.G., Chemical Abstracts, v01. 57, C01. l028lf, (1962).

Primary ExaminerBernard l-lelfin Assistant ExaminerMichael W. Glynn Attorney, Agent, or Firm-Francis W. Young; Jack H. Hall [57] ABSTRACT Plant hormone carboxylic acid salts of certain aliphatic diamines, triamines and tetraamines having at least 6 carbon atoms in an aliphatic radical thereof, useful as herbicidal agents.

8 Claims, No Drawings CROSS-REFERENCE TO RELATED APPLICATION This application is a continuation-impart of copending application Ser. No. 581,725, filed Sept. 26, 1966 now US. Pat. No. 3,683,010 which is a contiiiuationinpart of Ser. No. 300,108, filed Aug. 5, 1963, now abandoned.

Plant hormone carboxylic acids are believed to kill certain vegetation by stimulating the plants to excessive growth while having no unusual stimulating effect upon other vegetation. the use of such acids with other compounds, including aliphatic amines, has been found effective in controlling many types of weeds and other plants. One difficulty, however, has been the tendency for the product to volatilize in air currents and to be applied to plants which are-not intended to be destroyed. For example, it is common to apply the herbicide composition alongside roadways and adjoining crops, such as cotton, vegetable plants, etc., which must be protected from the action of the composition. Unfortunately, the herbicide composition can become airborne under the circumstances of spraying or other application, and serious damage to the beneficial plants is caused.

We have discovered that by reacting certain polyamines having at least 6 carbon atoms in an aliphatic radical with a plant hormone carboxylic acid, thus forming a salt, a highly effective herbicide, having substantially no tendency to volatilize in air currents, is obtained, thus permitting the composition to be sprayed all about a plant to destroy the weeds, etc., without injury to the plant. Not only does the composition become non-volatile so that it can be safely applied by spraying along a marginal area without danger of drifting, but also the composition has enhanced weedkilling values in providing better root penetration and slow-acting destruction.

A primary object of the invention, therefore, is to provide plant hormone carboxylic acid salts of higher aliphatic diamines, triamines and tetraamines which produce the above-described new results.

A further object is to provide certain diamine, triamine and tetraamine salts of herbicidal acids which are more oil-soluble and water soluble than previously available amine salts of herbicidal acids and which pro videa heavier molecule composition having little tendency to drift with air currents when applied by spraymg. v

A still further object is toprovide a polyamine salt herbicidal composition having unique properties enabling it tobeapplied around plants for the destruction of weeds without injuring the desired plant. Other spe- .cific objects and advantages will appear as the specification proceeds.

ln one embodiment of our invention, an aliphatic polyamine having preferably .from 6 to 23 carbon atoms in an aliphatic radical thereof is reacted with a plant hormone carboxylic acid to form a salt of the two substances. The resulting composition is oil soluble and can be applied in organic solvents, such as kerosene,

' xylene, aromaticoils,'acetone, diacetone, isopropanol,

etc. If desired, an oil-in-water emulsion may be formed and the composition applied in such an emulsion. The

application can be by spraying and, by way of specific example, it can be stated that the spray can be applied about a peony bush for destroying the weeds about the bush without contacting and injuring the peony plant.

and addition products of alkylene oxide selected from v the group consisting of ethylene oxide and propylene oxide in amounts of from about 1 to moles of alkylene oxide per mole of amine; and (11.) diamines selected from the group consisting of compounds having the formula wherein x is 0 to 15, y is 0 to 15, providedthat a: plus y is 3 to 15, and z is 0 to 2, R, R", R', and R"" are each selected from the group consisting of hydrogen, methyl, ethyl and addition products of alkylene oxide such as ethylene oxide and propylene oxide in the amounts of from 1 to 20 moles of alkylene oxide per mole of amine. Preferred diamines within the above formula are aminoundecylamine, aminostearylamine and aminornethylstearylamine wherein the remaining groups attached to the nitrogens are selected from the group consisting of hydrogen, methyl, ethyl and addition products of alkylene oxide selected from the group consisting of ethylene oxide and propylene oxide in amounts of from about 1 to 20 moles of alkylene oxide per mole of amine. v

The diamines may be obtained from fatty acids of natural fats or oils, such as tallow, soybean oil, cottonseed oil, coconut oil, or from fractions of these natural acid mixtures, saturated or unsaturated. Also, the diamines may be obtained from sources such as unsaturated acids and olefins. The long chain hydrocarbon radical may be straight chain or branched chain and saturated or unsaturated. The diamine may be allcoxylated with a compound such as ethylene or propylene oxide, either adding a fl-hydroxyalltyl group or a higher adduct thereof, preferably from about 1 to 20 molesof alkylene oxide per-mole of diamine. Especially preferred alkoxylation involves reaction of l to 6 moles of alkylene oxide per mole of diamine. H I Alkoxylatedaminesare well known'in the art to be produced by the reaction of an alkylene oxide such as ethylene oxide or propylene oxide with a primary or secondary amineqThe use of several moles of alkylene oxide per mole of amineresults in an alkylene oxide adduct having repeated ether linkages with a terminal hydroxy function. The random growth of an alkylene oxide adduct by addition of alkylene oxide to hydroxyl functions is well known in the art. Therefore, when more than the number of moles of alkylene oxide than free hydrogens available on nitrogen atoms are reacted with a polyamine a mixture of alkylene oxide adduct chain lengths is formed. the product thus formed is identified by the sum of the alkylene oxide units or the moles of alkylene oxide reacted with a mole of amine. Amines containing the beta hydroxethyl function at tached directly to the nitrogen atom have been found especially suitablefor use in this invention.

Preferred aliphatic polyamines include amines having an alkyl, alkenyl, or arylalkyl group containing from about 6 to 18 carbon atoms in the hydrocarbon chain. Suitable alkyl groups include hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, t'ridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, branched chain alkyl groups such as secondary alkyl including sec-alkyl C sec alkyl G sec-alkyl C and sec-alkyl C 5 One preferred subclass of secondary alkyl groups has the formula wherein x and y are integers of 0 to and the 'sum of x and y is an integer of 3 to 15. Other branched chain configurations are also suitable. Suitable alkenyl groups include hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, tridecenyl, tetradecenyl, pentadecenyl, hexadecenyl, heptadecenyl, octadecenyl and their branched chain derivatives. Mixtures of alkoxylated amines having both saturated and unsaturated groups such as'derived from coconut oil, tallow and other natural sources may be used.

Arylalkyl groups having the formula:

wherein x and y are integers of O to 15 and the sum of x and y is an integer 3 to 15, R is an aryl group selected from phenyl, naphthyl, and phenyl substituted with tions are well known in the art. The resultant triamine is the 'y-aminopropyl derivative of the diamine. In instance's'of diamines having two primary amino functions, the y-aminopropyl group may be added to either ainino function. In the case of diamines having one secondary and one. primary amino function, the 'y-aminopropyl group adds to the primary amino function m'akinga chain structure. All of the above disclosed diamines are suitable for formation of the triamine for use in' our invention. 7

Likewise, tetraamines may be produced by dicyanoethylation of diamines or -by monocyanoethylation of any of the previously mentioned tri-' amines. Especially preferred tetraamines are N- 'yaminopropyl, N'-'yaminopropyl aminostearylamine, aminomethylstearylamine, aminoundecylamine and aminomethylundecylamine. All of the above disclosed diamines and triamines are suitable for formation of the tetraamine for use in our invention.

The plant hormones occur generally in the form of carboxylic acids. Examples are 2,4 dichlorophenoxyacetic acid; 2,4,5-trichlorophenoxyacetic acid; methylchlorophenoxyacetic acid; chlorinated benzoic acid; dichloropropioriic acid; B-indolylacetic acid; a-naphthaleneacetic acid; indolylbutyric acid; indolylpropionic acid; phenylacetic acid; fluoroacetic acid; 2,5-dichloro-3-nitrobenzoic acid; 3-amino-2,5-dichloro benzoic acid, and 3,6-endoxohexahydrophthalic acid.

The reaction between the amine and the carboxylic acid may be carried out in any suitable manner. For example, the two substances may be mixed in a solvent and warmed until a homogeneous solution is obtained, and then cooled until precipitation of the salt is complete, after which it may be filtered and dried.

The resulting salts are viscous liquids which maybe then dissolved in organic solvents or emulsified to form oil-in-water emulsions, and the composition applied by spraying or by other suitable means to the area about the plants, etc.

' The following specific examples are illustrative of our invention. v

EXAMPLE I Various plant hormone carboxylic acid salts of differing molecular configurations of diamines, triamines and tetraamines were prepared by mixing stoichiometric proportions of polymamine and plant hormone carboxylic acid in benzene. The mixture was warmed to about to l00C until complete solution was obtained, agitated, then cooled, filtered and dried. The following products were prepared in this manner.

Dimethyl arsenic acid di salt of N-tallow trimethylenediamine (ethoxylated with 3 moles ethylene oxide). I 2,5-dichloro-3-nitrobenzoic acid mono salt of aminomethylstearylamine.

2,4-dichlorophenoxyacetic acid tri salt of N-tallow- N-('y-aminopropyl )-trimethylenediamine. 3-amino-2,5-dichlorobenzoic acid salt of aminomethylstearylamine. 3,6-endoxohexahydrophthalic acid mono and di salts of aminomethylstearylamine. 2,4-dichlorophenoxyacetic acid mono and di salts of aminomethylstearylamine. 3-amino-2,S-dichlorobenzoic acid di salt of N-tallow trimethylenediamine (ethoxylated with 3 moles ethylene oxide). 2,5-dichloro-3-nitrobenzoic acid di salt of'N-tallow trimethylenediamine (ethoxylated with 3 moles ethyleneoxide). 2,4-dichlorophenoxyacetic acid mono and di salts of N-(xylylstearyl) trimethylenediamine. 3,6-endoxohexahydrophthalic acid mono and di salts of N-(xylylstearyl) trimethylened iamine. 3,6,-endoxohexahydrophthalic acid mono and di salts of N,N,N',N' tetramethyl aminomethylstearylamine. v

2,4-dichlorphenoxyacetic acid mono and di salts of N,N,N',N' tetramethyl aminomethylstearylamine.

3,6-endoxohexahydrophthalic acid mono and di salts pre-emergence application of chemical at the indicated application rate and observed 20 days post application.

It should be noted that the 2.4-dichlorophenoxyaof N-(phenylbehenyl) trimethylenediamine. cetic acid mono salt of both aminostearylamine and 2,4-dichlorophenoxyacetic acid mono and di salts of phenyl-stearyl trimethylenediamine of this invention N-(phenylbehenyl) trimethylenediamine. afford complete safety to soybeans while effectively 2,4-dichlorophenoxyacetic acid tri salt of N-oleyl-N- controlling weeds, while the 2,4-dichlorophenoxya ('y-arninopropyl)-trimethylenediamine cetic acid mono salt of N-tallow trimethylenediamme a,o -dichl0ropropi0nic acid mon d di lt f N. kills the soybeans while not efllectlvely controlling (C C sec-alltyl) trimethylenediamine (ethoxyl- Weeds at the a pph lon rate.

TABLE 1 Chemical Pounds 'ln'ur Ratin 3 Weeds Per Soy- Sugar Spin String Broad- I ucum- Acre Corn bean Cotton Beet ach Wheat Bean ber leaf Grass 2,5-dichloro-3-nitrobenzoic l 0 5 8-D l0 l0 acid mono salt of amino- 2 0 0 1 9 0 5 5-D 9 4 methylstearylamine 4 0 1-D 2 9 5 l0 2 3-amino2,S-dichlorobenzoic l 9 4-D 0 l0 l0 acid di salt of N-sec-tridecyl 2 0 5 2 0 O 2 2 3 9 7 trimethylenediamine (ethoxy- 4 0 8 0 l 3 0 2 4 lated with 3 moles ethylene oxide) 2,4-dichlorophenoxyacetic 0.75 0 l 0 O 0 O 9 6 acid mono salt of amino- 2 0 O 0 l O 0 8 5 methylstearylamine 2.4-dichlorophenoxyacetic 0.75 0 3-D l 4 l-D 9 3 acid di salt of amino- 2 0 2 0 0 3 l0 5 metbylstearylamine 2,4-dichlorophenoxyacetic l .0 0 O 0 l0 acid mono salt of amino- 0.5 O 0 O 9 stearylamine 2,4-dichlorophenoxyacetic 1.0 0 0 0 [0 acid mono salt of N-pheny|- 0.5 0 0 0 9 stearyl lrimethylenediamine 2,4-dichlorophenoxy acetic 1.0 3 l0 0 7 acid mono salt of N-tallow 0.5 0 l0 0 8 trimethylenediamine Rating 0=No injury; l=Slight injury; 5=Moderate injury; 9=Very heavy injury; l0=Plants dead; D=Dwarfcd ated with 3 moles ethylene oxide).

ma-dichloropropionic acid mono and di salts of N- tallow trimethylenediamine (ethoxylated with 10 moles ethylene oxide).

3,6-endoxohexahydrophthalic acid mono and di salts of N,N,N',N tetraethyl aminostearylamine.

2,4-dichlor0phenoxyacetic acid mono and di salts of N-tallow trimethylenediamine (propoxylated with 10 moles propylene oxide).

EXAMPLE ll Diamine salts of plant hormone carboxylic acids were applied to various crops and weeds to ascertain their selective herbicidal action. Table I shows the results of EXAMPLE Ill following spray application the number of germinatingsoybean plants and the number of soybean plants show ing any injury was noted. Twelve days following spray application the percent weed control was noted. Twenty soybean seeds were planted in each flat. Table ll shows the good weed and grass control obtained with very low injury to the desired soybean crop.

TABLE ll Weed Control RATE EIGHT DAYS 12 DAYS Number Number Broadleaf Chemical Lbs/Acre Germinated Injured Weeds Grass 2,4-dichlorophenoxyacetic 1.0 20 2 99 95 acid mono salt of N-phenyl- 0.5 20 3. 88 stearyl trimethylenediamine 2,4-dichIorophenoxyacetic 1.0 l7 0 90 99 acid mono salt of 9(10) amine 0.5 19 l 70 98 stearylamine EXAMPLE W The 2,4-dichlorophenoxyacetic acid mono salts and di salts of aminomethylstearylamine were prepared and applied by a water spray to flats seeded with alfalfa, crabgrass and pigweed. The herbicide was applied at the rate of 0.5 lbs. of active herbicide per acre. The flats were observed after 18 days and it was noted that the desired alfalfa crop emerged at a high rate while the undesired weeds were effectively killed. The results are Diamine salts of plant hormone carboxylic acids were applied in aqueous sprays post emergence to different crops and weeds to illustrate their effective and selective herbicidal action. Table IV; shows the results of post-emergence application of specified chemicals observed 7 days after application of the herbicide.

TABLE iv stood that such detail or details may be varied widely by those skilled in the art without department from the compounds of our invention is shown by the water solu bility of 2,4-dichlorophenoxyacetic acid fully neutralized salts of various polyamines. The solubilities were obtained by using tap water having a pH 8.4 and at 25C.

Amine Salt Solubility Per Cent N-phenylstearyltrimethylene diam'ine 0.0004

N -oleyl trimethylene diamine 0.0002

N-tallow, Nqaminopropyl trimethylene diamine 0.01

N-'yaminoptopyl, N'-amin0propyl aminostearylamine 0.03

N-tallow, N'--yaminopropyl, N"- aminopropyl,

trimethylene diamine 0.06

9( l0)-aminomethyl-stearylamine 0.07

While in the foregoing specification we have set forth illustrative embodiments in considerable detail for the purpose of explaining the invention, it will be underspirit of our invention.

We claim:

1. A plant hormone carboxylic acid salt of an aliphatic polyamine selected from the group consisting of pounds which :have a'ctivehydrogens on the amino groups. Specific control water solubility of certain Weeds Pounds Injury Rating Broad Chemical Per Acre Corn Wheat Leaf Grass 2,4-dichlorophenoxyacetic 0.5 0 0.5 8 0 acid di salt of aminomethyll 2 0.5 9.5 0 stearyl amine 2,4-dichlorophenoxy acetic 0.5 0 l 9 0 acid mono salt of aminoinethyl l 3 I l0 0 stearyl amine EXAMPLE VI aminostearylamine, aminomethylstearylamine, amione mole of NN, di(,y amin0pmpy1) noundecylamine, and aminomethylundecylamine and 'y-aminopropyl derivatives thereof having the following aminomethylstearylamme (50% active in isopropanol) formula was warmed to about 70C and 4 moles of 2,4-dichlorophenoxyacetic acid were added slowly. During this addition the temperature was maintained at about 70 to 80 C and agitation was provided by a nitrogen sparger H until the reaction was complete. The product was the cin-(cn,).0n o1r, -oinN 2,4-dichlorophenoxyacetic acid tetra salt of N,N'-'di('y- (CH) R aminopropyl)-aminomethylstearylamine. 1 I z This chamical is effective in control of weeds as a selective pre-emer gence herbicide. H Whileall of the plant hormone carboxylic acid salts of aliphatic polyamines of our invention are generally soluble in oils, the compounds of our invention afford wherein the surprising property of controlled increased water x O to 15 solubility. Controlled water solubility is desirable for y 0 to 5 increased soil penetration and to facilitate plant metabz or 1 olism'of the compounds. Slow controlled water solubilx y 3 or 15 I ity is'also desirable to obtain effective and continued R, R" H or y -aminopropyl a tic weed control. The alkoxylated polyamines 0f said plant hormone carboxylic acid being selected from our invention, such as the ethylene oxide adducts and the group consisting of 2,4-dichlorophenoxyacetic the propylene oxide adducts, have increased water solacid; 2,4,5-trichlorophenoxyacetic.a id; th l hl ubility as compared 'with their corresponding comphenoxyacetic acid; chlorinated benzoic acid; di-

chloropropionic acid; B-indolylacetic acid a-naphthaleneactic acid; indolylbutyric acid; indolylpropionic 3,852,340 9 W acid; phenylacetic acid; fluoroacetic acid; 2,5dichlorowherein the polyamine is aminomethylstearylamine. 3-nitr0benzoic acid; 3-amino-2,S-dichlorobenzoic acid, 6. Th plant hormone carboxylic acid salt of claim 5 and 3i6'endoxohexahydrophthalic acidwherein said carboxylic acid is 2,4-dichlorphen0xya- 2. A plant hormone carboxylic acid salt of a polyi cetic acid.

amine of claim 1 wherein said polyamine 1s a trlamine. 5 A plant hormone carboxylic acid salt of Claim 11 3. A plant hormone carboxylic acid salt of apolywhrem salld p9lyammel N amine of claim ll wherein said polyamine is a tetraaammopropy ammosteary amme" mine. 8. A plant hormone carboxylic acid salt of claim 1 i. A Plant hormone carboxylic acid salt of claim 1 10 wherein S PP NV' p py wherein-the polyamine is aminostearylamine. aminopropyl aminoundecylamme.

5 A plant hormone carboxylic salt of claim I 

1. A PLANT HORMONE CARBOXYLIC ACID SALT OF AN ALIPHATIC POLYAMINE SELECTED FROM THE GROUP CONSISTING OF AMINOSTEARYLAMINE, AMINOMELTHYLSTEARYLAMINE, AMINOUNDECYLAMINE, AND AMINOMETHYLUNDECYLAMINE AND Y-AMINOPROPYL DERIVATIVES THEREOF HAVING THE FOLLOWING FORMULA:
 2. A plant hormone carboxylic acid salt of a polyamine of claim 1 wherein said polyamine is a triamine.
 3. A plant hormone carboxylic acid salt of a polyamine of claim 1 wherein said polyamine is a tetraamine.
 4. A plant hormone carboxylic acid salt of claim 1 wherein the polyamine is aminostearylamine.
 5. A plant hormone carboxylic salt of claim 1 wherein the polyamine is aminomethylstearylamine.
 6. The plant hormone carboxylic acid salt of claim 5 wherein said carboxylic acid is 2,4-dichlorophenoxyacetic acid.
 7. A plant hormone Carboxylic acid salt of claim 1 wherein said polyamine is N- gamma -aminopropyl, N''- gamma -aminopropyl aminostearylamine.
 8. A plant hormone carboxylic acid salt of claim 1 wherein said polyamine is N- gamma -aminopropyl, N''- gamma -aminopropyl aminoundecylamine. 